Nanolaminate Coatings

ABSTRACT

This disclosure includes coatings for increasing the physical and/or chemical properties of articles, for example, tubular metal articles such as those found in the oil and gas industry, as well as processes for making such coatings and articles comprising such coatings.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional PatentApplication No. 61/802,301, filed Mar. 15, 2013, which application isincorporated herein by reference in its entirety.

FIELD

This disclosure includes coatings for increasing the physical and/orchemical properties of articles, for example, tubular metal articlessuch as those found in the oil and gas industry, as well as processesfor making such coatings and articles comprising such coatings.

SUMMARY

This disclosure describes coatings comprising nanolaminates that may beapplied to articles, including steels and polymeric substrates forexample, to improve their physical and/or chemical properties. Processesfor making such coatings and articles comprising such coatings are alsodisclosed. Embodiments of this disclosure include tubular articlescomprising such coatings, for example, tubular materials used in the oiland gas industry such as casings, drill pipes and the like.

FIGURES

FIG. 1 illustrates a schematic of a testing apparatus used for collapsepressure measurement.

FIG. 2 is a plot of collapse performance for steel alloy pipe andnickel-cobalt nanolaminate coated steel pipe at various Diameter/wallThickness (D/T) ratios versus their collapse pressures along with BladeCalculated values.

FIG. 3 is a plot of collapse performance for steel alloy pipe andnickel-cobalt nanolaminate coated at steel pipe at various D/T ratiosversus their collapse pressures along with finite element analysis (FEA)model predictions.

DESCRIPTION 1.0 Overview

Electrodeposited nanolaminate coatings are provided to improve one ormore properties of materials, including tubular materials and inparticular tubular materials comprising iron based alloys. Embodimentsdisclosed herein include the use of nanolaminate coatings comprisingnickel and cobalt to improve the properties of tubular items such asthose used in oil and gas drilling and production (e.g., goods, such ascasings, drill pipe, and the like). Other embodiments of the coatedarticles comprise tubular materials made from non-metallic materialssuch as plastics, ceramics, polymeric composites, etc.

2.0 Definitions

“Laminate” or “laminated” as used herein refers to materials thatcomprise a series of layers, including nanolaminated materials.

“Nanolaminate” or “nanolaminated” as used herein refers to materials orcoatings that comprise a series of layers less than 1 micron.

Percentages, unless stated otherwise, are percentage by weight.

3.0 Articles

The articles that can be improved by the coatings of this disclosureinclude conductive metallic and non-metallic substrates, includingespecially conductive metallic and non-metallic tubular articles such asthose used in oil and gas drilling and production, e.g., goods, casings,drill pipe, and the like, including such products made from steel andalso from polymer composite materials such as m-Pipe™, a polymer-carbonfiber composite made from PEEK polymer (produced by Magma).

In embodiments, conductive articles may comprise a conductive ornon-conductive polymeric composition and may comprise one or more metalsor non-metallic conductive materials added to the polymers (e.g., beforeor after curing) that render the composition conductive or moreconductive. Examples of conductive, non-metallic materials that can beadded to polymers to increase conductivity are carbon black, graphene,graphite, carbon nanotubes, carbon nanofibers, or graphite fibers, whichcan be added to the polymers alone or in combination with conductivemetallic materials.

A variety of conductive polymeric materials can thus be used to preparearticles having improved properties according to this disclosure,including tubular articles.

4.0 Nanolaminate Coatings

The composition comprising a metal that is electrodeposited onto thearticle may vary in its constituent metals. In some embodiments, thecomposition comprises one or more, two or more, three or more, or fouror more different metals independently selected from Ag, Al, Au, Be, Co,Cr, Cu, Fe, Hg, In, Mg, Mn, Mo, Nb, Nd, Ni, Pd, Pt, Re, Rh, Sb, Sn, Mn,Pb, Ta, Ti, W, V, Zn and Zr, wherein each of said independently selectedmetals is present at greater than 0.1, 0.05, 0.01, 0.005 or 0.001% byweight. In such embodiments, compositions of two or more differentmetals that can be electrodeposited comprise, for example, Zn and Fe, Znand Ni, Co and Ni, Ni and Fe, Ni and Cr, Ni and Al, Cu and Zn, or Cu andSn.

In some embodiments, the composition electrodeposited onto the articlecomprises a structurally and/or compositionally modulatedelectrodeposited material or composition. The structurally and/orcompositionally modulated composition may comprise at least one portionhaving a plurality of layers deposited with wavelengths between about 1nm and about 250 nm, about 1 nm and about 25 nm, about 5 nm and about 50nm, about 10 nm and about 75 nm, about 1 nm and about 100 nm, about 2 nmand about 200 nm, about 5 nm and about 225 nm, about 10 nm and about 250nm.

In other embodiments, the structurally and/or compositionally modulatedmaterial has at least one portion consisting of a plurality of layers,wherein each of said layers has a thickness in a range selectedindependently from about 5 nm to about 250 nm, from about 5 nm to about25 nm, from about 10 nm to about 30 nm, from about 30 nm to about 60 nm,from about 40 nm to about 80 nm, from about 75 nm to about 100 nm, fromabout 100 nm to about 120 nm, from about 120 nm to about 140 nm, fromabout 140 nm to about 180 nm, from about 180 nm to about 200 nm, fromabout 200 nm to about 225 nm, from about 220 nm to about 250 nm, or fromabout 150 nm to about 250 nm.

Multilayer nanolaminate coatings may comprise a large number of layers.The coatings may comprise two or more, three or more, four or more, sixor more, eight or more, ten or more, twenty or more, forty or more,fifty or more, 100 or more, 200 or more, 500 or more, 1,000 or more,1,500 or more, 2,000 or more, 2,500 or more, 3,000 or more, 3,500 ormore, 4,000 or more, 5,000 or more, 6,000 or more, 7,000 or more, or8,000 or more layers (e.g., first and second layers each countedseparately as a layer). The number of layers may be independentlyselected for each nanolaminate coating present on different portions ofan article (e.g., the inside and outside of a pipe may have differentcoatings applied). The overall number of layers in a coating may also bein a range from about 100 to about 8,000, from about 50 to about 100,from about 100 to about 1,000, from about 1,000 to about 2,000, fromabout 2,000 to about 4,000, from about 4,000 to about 8,000 layers, orgreater than about 8,000 layers.

The overall thickness of the nanolaminate coatings may vary widelydepending on the application of the coatings. In some embodiments, thecoatings may have a thickness in a range selected independently from 1micron to 5 cm, from 1 micron to 50 microns, from 50 microns to 100microns, from 100 microns to 200 microns, from 200 microns to 500microns, from 500 microns to 800 microns, from 800 microns to 1.2 mm,from 500 microns to 1 mm, from 1 mm to 1.5 mm, from 1.2 mm to 2 mm, from1.8 mm to 2.5 mm, from 2 mm to 3 mm, from 2.5 mm to 5 mm, from 1 mm to 5mm, from 5 mm to 1 cm, from 1 cm to 2 cm, or from 2 cm to 5 cm.

As described above, where the electrodeposited material comprises two ormore structurally and/or compositionally different layers, the layersmay have discrete or diffuse interfaces or combinations of discrete anddiffuse interfaces.

In embodiments where the electrodeposited material comprises two or morestructurally and/or compositionally different layers, the compositionmay comprise a plurality of alternating first layers and second layers.The coating of electrodeposited material may consist entirely of thealternating first and second layers, which may have discrete or diffuseinterfaces between the layers or. Alternatively, one or more additionallayers may be present in the coating between any first and second layer.The first and second layers may be the same throughout or may themselveschange in composition and/or structure, and the interfaces (e.g.,discrete or diffuse), may change from layer to layer or between groupsof layers.

In embodiments described herein, nanolaminate coatings for improving theproperties of articles and goods, including those used in oil and gaswell drilling and production, may comprise multilayer coatingscomprising nickel and cobalt. In some embodiments, a plurality ofalternating first layers of nickel or an alloy comprising nickel, andsecond layers of an alloy comprising nickel and cobalt are combined toform a coated article. Other layers may be included in addition to thefirst and second layers.

In some embodiments, first layers each may comprise an amount of nickelgreater than about 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 92%,93%, 94%, 95%, 96%, 97%, 98% or 99%. For all such first layers, theamount of nickel in each layer is independently selected and may bevaried from layer to layer or among groups of layers. In someembodiments, each first layer comprises nickel in a range selectedindependently from 50%-55%, 55%-60%, 60%-65%, 65%-70%, 70%-75%, 75%-80%,80%-85%, 85%-90%, 90%-92%, 92%-93%, 93%-94%, 94%-95%, 95%-96%, 96%-97%,97%-98% or 98%-99%, and the balance or the substantial part of thebalance of the layer may comprise cobalt. In other embodiments, eachfirst layer comprises nickel in a range selected independently from70%-99%, 70%-75%, 75%-80%, 80%-85%, 85%-90%, 90%-92%, 92%-93%, 93%-94%,94%-95%, 95%-96%, 96%-97%, 97%-98% or 98%-99%, and the balance or thesubstantial part of the balance of the layer may comprise cobalt. Instill other embodiments, each first layer comprises nickel in a rangeselected independently from 50%-55%, 55%-60%, 60%-65%, 65%-70%, 70%-75%,75%-80%, 80%-85% or 85%-90%, and the balance or the substantial part ofthe balance of the layer may comprise cobalt.

In such embodiments, second layers may each comprise an amount of cobaltin a range independently selected from 5%-35%, 5%-10%, 10%-15%, 15%-20%,20%-25%, 25%-30% or 30%-35% cobalt. As with the first layers, the amountof cobalt in each second layer is independently selected and may bevaried from layer to layer or among groups of layers. In suchembodiments each second layer comprises cobalt in a range selectedindependently from 5%-35%, 5%-10%, 10%-15%, 15%-20%, 20%-25%, 25%-30%,or 30%-35% and the balance or the substantial part of the balance of thelayer may comprise nickel. In other embodiments, each second layercomprises cobalt in a range selected independently from 20%-35%,20%-25%, 25%-30% or 30%-35% and the balance or the substantial part ofthe balance of the layer may comprise nickel. In yet other embodimentseach second layer comprises cobalt in a range selected independentlyfrom 5%-20%, 5%-10%, 10%-15% or 15%-20%, and the balance or thesubstantial part of the balance of the layer may comprise nickel.

In embodiments of this disclosure, each first and/or second layer maycomprise, consist essentially of, or consist of nickel and cobalt andinsubstantial amounts of other components (e.g., less than 0.1%, 0.05%or 0.01% of other component elements, taken individually). Inembodiments of this disclosure, in addition to their nickel and cobaltcontent, each first and second layer may comprise one or more, two ormore, three or more, or four or more additional elements selectedindependently for each first and second layer from the group consistingof Ag, Al, Au, Be, C, Cr, Cu, Fe, Hg, In, Mg, Mn, Mo, Nb, Nd, P, Pd, Pt,Re, Rh, Sb, Si, Sn, Pb, Ta, Ti, W, V, Zn and Zr. In other suchembodiments, in addition to their nickel and cobalt content each firstand second layer may comprise one or more, two or more, three or more,or four or more additional elements selected independently for eachfirst and second layer from the group consisting of Ag, Al, C, Cr, Cu,Fe, Mg, Mn, Mo, Nb, P, Sb, Si, Sn, Ti, W, V, Zn and Zr; or from thegroup consisting of Al, C, Cr, Fe, Mg, Mn, Mo, Si, Sn, Ti, W, V, and Zn.In some embodiments, additional elements that are present will bepresent at greater than about 0.1% in order not to be considered aninsubstantial amount of the component.

As mentioned above, the coating may comprise additional layers inaddition to the first and second layers. Such additional layers maycomprise any materials as disclosed herein.

In other embodiments where a plurality of first and second layers arepresent, the first layers may each comprise zinc in a rangeindependently selected from 1%-5%, 5%-7%, 7%-10%, 10%-15%, 15%-20%,20%-30%, 30%-40%, 40%-50%, 50%-55%, 55%-60%, 60%-65%, 65%-70%, 70%-75%,75%-80%, 80%-85%, 85%-90%, 90%-92%, 92%-93%, 93%-94%, 94%-95%, 95%-96%,96%-97%, 97%-98% or 98%-99%, the balance or substantial part of thebalance of which may comprise another element such as iron. In suchembodiments, each second layer may comprise iron in a rangeindependently selected from 1%-35%, 1%-3%, 2%-5%, 5%-10%, 10%-15%,15%-20%, 20%-25%, 25%-30%, or 30%-35%, the balance or substantial partof the balance of which comprises zinc.

In other embodiments where a plurality of first and second layers arepresent, the first layers each may comprise copper in a rangeindependently selected from 1%-5%, 5%-7%, 7%-10%, 10%-15%, 15%-20%,20%-30%, 30%-40%, 40%-50%, 50%-55%, 55%-60%, 60%-65%, 65%-70%, 70%-75%,75%-80%, 80%-85%, 85%-90%, 90%-92%, 92%-93%, 93%-94%, 94%-95%, 95%-96%,96%-97%, 97%-98% or 98%-99%, the balance or substantial part of thebalance of which may comprise zinc and/or tin. In such embodiments, eachsecond layer comprises zinc and/or tin in a range independently selectedfrom 1%-35%, 1%-3%, 2%-5%, 5%-10%, 10%-15%, 15%-20%, 20%-25%, 25%-30% or30%-35%, the balance or substantial part of the balance of whichcomprises copper.

In embodiments where the components of the above-mentionedelectrodeposited compositions are not completely defined (that is, lessthan 100% of the components by weight are defined and/or required), thenthe balance of those layers may comprise one or more different elements.That is particularly so in embodiments of the above-mentioned binary orternary alloy compositions comprising a plurality of layers (e.g., offirst and second layers). Thus, in some embodiments, theelectrodeposited compositions may comprise one or more elements selectedfrom the group consisting of Ag, Al, Au, Be, C, Cr, Cu, Fe, Hg, In, Ir,Mg, Mn, Mo, Nb, Nd, Pd, Pt, Re, Rh, Sb, Si, Sn, Pb, Ta, Ti, W, V, Zn andZr. In other embodiments, where the electrodeposited compositioncomprises one or more of said first and/or second layers, the layers mayeach comprise one or more, two or more, three or more, or four or moreelements selected independently for each first and second layer from thegroup consisting of Ag, Al, Au, Be, C, Cr, Cu, Fe, Hg, In, Mg, Mn, Mo,Nb, Nd, Pd, Pt, Re, Rh, Sb, Si, Sn, Pb, Ta, Ti, W, V, Zn and Zr.

5.0 Nanolaminate Coating Structure and Orientation

Regardless of which nanolaminate coating is employed to improve theproperties of an article, the nanolaminate coating composition may beoriented so that a first layer or second layer is in contact with thesubstrate on which the coating is applied (e.g. the surface of a pipe).Thus in some embodiments a first layer is in contact with the surface onwhich the electrodeposited coating is applied, and in other embodimentsthe second coating is in contact with the surface of the substrate. Thelayer in contact with the surface of the substrate may affect theadhesion of the coating and any corrosion resistance. Because differentcoatings may be applied to different portions of the same article (e.g.,the inside and outside of a pipe or other tube may have differentcoatings), it will be understood that the different coatings may beoriented differently (i.e., in one coating a first layer contacts asubstrate and in a coating applied on a different part of the samearticle a second layer contacts a substrate).

6.0 Properties of Electrodeposited Coatings and Articles

Electrodeposited alloys applied to articles (e.g., nanolaminatecoatings) can be fully or substantially fully dense, having a limitednumber of pores or cracks, making them useful as corrosion resistantcoatings, in addition to their role as a structural component offinished parts or objects.

In embodiments where the electroplated compositions are comprised of aplurality of layers less than about 20 nm (e.g., about 15 nm, 10 nm, 8nm, or 5 nm), the compositions display increased “Hall-Petch”hardness/toughness and strength. The observed increases in hardnessresults from grain confinement and increased toughness results fromforce reflection in the laminate regions. Such coatings tend to followthe Hall-Petch relationship, which traditionally is used to describe theincrease in yield strength observed in nanocrystalline materials.

In embodiments where the electroplated compositions are comprised of aplurality of layers of hard and soft materials laminated together, theelectrodeposited composition may display Koehler toughening. That formof toughening results from a deflection of a nascent crack at the layerinterface due to differing modulus. Such objects can thus absorb theenergy that typically causes cracking and thereby prevent orsubstantially diminish bulk material failure, and/or prolong the time tosuch bulk material failure.

In addition to mechanical and physical enhancement of articleproperties, compositions electrodeposited onto articles also can alterthe articles' chemical attributes. In some embodiments, at least aportion of the composition electrodeposited onto a article is chemicallyresistant to the environment and protects the underlying article (e.g.,the metal coating protects the article from solvents or UV light thatmay damage the article). In other embodiments, at least a portion of thecomposition electrodeposited on the article is more noble than theunderlying article and acts as a barrier coating in corrosiveenvironments that can damage the underlying article. In yet otherembodiments, at least a portion of the composition electrodeposited onthe article is less noble than the article and sacrifices itself incorrosive environments to protect the article.

Where the properties of pipes, tubes and other items having tubularelements are to be improved, the coating thickness may be in the rangefrom less than about 5% to about 25% or more (e.g., from less than 5% to5%, from about 5% to about 10%, from about 10% to about 15%, from about15% to about 20%, from about 20% to about 25%, or more than 25%) of thewall thickness of those items. In such ranges, pipes, tubes, and tubularelements can exhibit a marked increase in performance. In someembodiments, pipes or tubes comprised of steel alloys, display a markedimprovement their properties, including burst pressure, collapsepressure, or force displacement (crushing force).

Depending on the D/T ratio and thickness and composition of thenanolaminate coating, the burst pressure, collapse pressure and/or forcedisplacement (crushing force) of the externally coated pipe is increasedfrom about 5% up to 100% or more relative to an uncoated pipe havingsubstantially the same composition and substantially the same D/T ratioas the coated pipe. Hence increases in the burst pressure, collapsepressure, or force displacement (crushing force) of about 5 to about10%, about 10 to about 15%, about 15 to about 20%, about 20 to about25%, about 25 to about 30%, about 30 to about 35%, about 35 to about40%, about 40 to about 45%, about 45 to about 50%, about 50 to about60%, about 60 to about 70%, about 70 to about 80%, about 80 to about90%, about 90 to about 100% and over 100% can be obtained relative to anuncoated pipe having substantially the same composition andsubstantially the same D/T ratio as the coated pipe.

6.1 Properties of Nickel-Cobalt or Nickel-Chromium Coated Materials.

In addition to nickel and cobalt containing first and second layers, thecoatings may comprise additional layers, such as a coating ornanolaminate coating of NiCr alloys to increase improve the tribologicalproperties and/or chemical resistance of the overall coating.

Improving the properties of articles with nickel-cobalt ornickel-chromium containing nanolaminate coatings can provide the articlea variety of desirable properties including, but not limited to,increased hardness, strength, wear resistance, and corrosion resistance.

In one series of embodiments, where pipes, tubes and other items havingtubular elements are to be coated, the resulting article can exhibitincreases in its collapse and/or burst pressure.

In embodiments where the article is a pipe or tube formed from steel, asteel alloy comprising: carbon, iron, molybdenum, or an alloy comprisingcarbon, iron, molybdenum and cobalt (such as American PetroleumInstitute L80, C95, P110 or Q125 grade steels or American Iron and SteelInstitute 4130, 4135, 4137, 4140, or 4145 steels) the nanolaminatednickel-cobalt or nickel-chromium coatings described herein can markedlyimprove the performance of the tubes and pipes in burst and collapsepressure tests. In embodiments where the nanolaminated nickel-cobaltcoatings are applied only to the exterior surface of the pipe and theyhave a coating thickness from about 5% to about 25% of the wallthickness (e.g., less than 5%, from about 5% to about 10%, from about10% to about 15%, from about 15% to about 20%, from about 20% to about25%, or greater than 25% of the wall thickness), the performance exceedswhat would be expected from the properties of the separate materials byfinite element analysis (FEA) when the data are corrected for changes inthe D/T ratio (i.e., the additional thickness of the pipe is included inthe measurement). For pipes with typical wall thicknesses in the rangeof about 0.2 inches to about 0.65 inches, the coating thickness may befrom about 10 thousandths to about 160 thousandths of an inch (about0.25 mm to about 4 mm), but may be either thinner or thicker.

In such embodiments when the D/T ratio is from about 14 to about 15 theburst pressure and/or collapse pressure of the externally coated pipe isincreased from about 5% to about 22%, from about 5% to about 10%, fromabout 10% to about 15% or from about 15% to about 22% relative to anuncoated pipe having substantially the same composition andsubstantially the same D/T ratio as the coated pipe.

Where the D/T ratio is from about 15 to about 21 the burst pressureand/or collapse pressure of the externally coated pipe is increased fromabout 10% to about 36%, from about 10% to about 15%, from about 15% toabout 20%, from about 20% to about 25%, from about 25% to about 30%, orfrom about 30% to about 36% relative to an uncoated having substantiallythe same composition and substantially the same D/T ratio as the coatedpipe.

Depending on the D/T ratio and thickness and composition of thenickel-cobalt or nickel-chromium nanolaminate coating, increases in theburst pressure, collapse pressures and/or force displacement (crushingforce) of the externally coated pipe is increased from about 5% up to100% or more the relative to an uncoated having substantially the samecomposition and substantially the same D/T ratio as the coated pipe.Hence increases in the burst pressure, collapse pressures, or forcedisplacement (crushing force) of about 5 to about 10%, about 10 to about15%, about 15 to about 20%, about 20 to about 25%, about 25 to about30%, about 30 to about 35%, about 35 to about 40%, about 40 to about45%, about 45 to about 50%, about 50 to about 60%, about 60 to about70%, about 70 to about 80%, about 80 to about 90%, about 90 to about100% and over 100% can be obtained relative to an uncoated havingsubstantially the same composition and substantially the same D/T ratioas the coated pipe.

In some embodiments a steel pipe having a D/T ratio of about 15 and ananolaminated nickel-cobalt or nickel-chromium coating on its exteriorsurface from about 50 to about 70 thousandths of an inch thick has acollapse pressure greater than about 13,000 psi.

In some embodiments a steel pipe having a D/T ratio of about 16 and ananolaminated nickel-cobalt or nickel-chromium coating on its exteriorsurface from about 50 to about 70 thousandths of an inch thick has acollapse pressure greater than about 11,000 psi.

In some embodiments a steel pipe having a D/T ratio of about 17 and ananolaminated nickel-cobalt or nickel-chromium coating on its exteriorsurface from about 50 to about 70 thousandths of an inch thick has acollapse pressure greater than about 10,500 psi.

In some embodiments a steel pipe having a D/T ratio of about 18 and ananolaminated nickel-cobalt or nickel-chromium coating on its exteriorsurface from about 50 to about 70 thousandths of an inch thick has acollapse pressure greater than about 9,750 psi.

In some embodiments a steel pipe having a D/T ratio of about 19 and ananolaminated nickel-cobalt or nickel-chromium coating on its exteriorsurface from about 50 to about 70 thousandths of an inch thick has acollapse pressure greater than about 9,000 psi.

The nickel-cobalt or nickel-chromium coatings may also function ascorrosion barriers imparting resistance to corrosion of underlyingsubstrates (e.g., susceptible materials such as steels) by acids, bases,H₂S and the like.

7.0 Electrodepositon of Coatings 7.1 Pretreatment of Conductive orNon-Conductive Articles

In order to electrodeposit a composition comprising a metal on at leasta portion of an article surface that is accessible to liquids, e.g., atubular article, the surface must be conductive and brought in contactwith a bath containing salts of the metals to be electrodeposited. Tomake the surface of a non-conductive article conductive, or to increasethe conductivity of an article that is already conductive, typicallyrequires subjecting the surface to electroless plating of a metal suchas nickel, cadmium, gold, silver, rhodium, chrome, zinc, tin, or copper.In some embodiments, the metal applied to the article by electrolessdeposition is nickel.

Preparation of articles for electroless plating, particularly ofnon-conductive plastic/polymer articles such as tubular articles,generally includes a step of etching the surface of the article. Etchingis typically accomplished by using a strong oxidizing agent to createmicroscopic pores or holes in the surface of the plastic. The pores orholes increase the surface area and improve adhesion of subsequentlyapplied metal layers. Some strong oxidizing solutions/suspensions usedas etchants include peroxides (e.g., hydrogen peroxide), persulfates,chromic acid, acidic or basic permanganate solutions, chromium trioxidesolutions or suspensions, and sulfuric acid. In embodiments, the articlecomprises a tube made from ABS and the etchant is chromic acid orchromium trioxide containing solution/suspension.

Following etching, at least a portion of the etched section of thearticle may be contacted with a composition that deposits a metalliccatalyst on the etched surface of the polymeric article. The catalyst istypically palladium, which can be applied using tin as a reducing agent(e.g., Sn⁺²+Pd⁺²=Sn⁺⁴Pd⁰), however, other catalysts including noblemetal catalysts may be used (e.g., platinum, rhodium, iridium, nickel,copper, silver, gold). Upon contact with the electroless plating bath,the catalyst causes a layer of metal to form on the surface of thepolymeric article exposed to the catalyst and then the bath.

7.2 Electrodeposition

Metals, polymers, and semiconductors can all be electroplated(electrodeposited), and in most cases the required conditions are at ornear ambient temperature and pressure. Embodiments of the processesdescribed herein include methods of electrodepositing a compositioncomprising a metal on an article prepared by additive manufacturing,where the process comprises:

a) optionally subjecting all or part of the article to electrolessplating;

b) providing a bath including at least one electrodepositable component;

c) contacting all or part of the article with the bath; and

d) applying voltage or current to the article to deposit at least oneelectrodepositable component comprising a metal.

In some embodiments, the bath comprises at least two, at least three, orat least four electrodepositable components. The electrodepositablecomponents include metal salts, from which metals may be electroplatedonto the article, and where the bath comprises more than one metal saltas an electrodepositable component, alloys of varying composition may beelectrodeposited on the article depending on the current and voltageapplied.

In some embodiments, the method of electrodepositing comprises applyinga time varying current density, wherein the time varying current densityoscillates at least for two cycles to deposit a structurally and/orcompositionally modulated material on the article. The structural and orcompositionally modulated material may be applied such that it has adiscrete interface, or a diffuse interface, where the compositionchanges from a first composition to a second composition over a distancefrom about 3 nm to about 8 nm, about 5 nm to about 10 nm, about 7 nm toabout 15 nm or about 10 nm to about 20 nm. In other embodiments, adiscrete interface between two layers may be considered as one in whichthe composition shifts between the compositions of the first layer andthe second layer over a distance that is less than about 20%, about 15%,about 10%, about 8%, about 5%, about 4% or about 2% of the thickness ofthe thinner of the first and second layers. In other embodiments layershave diffuse interfaces where the compositions vary from that of a firstcomposition to a second composition in a continuous manner. In someembodiments, the diffuse interface varies between the compositions ofthe first and second layer over a distance that is greater than about20%, about 25%, about 30%, about 35%, about 40% or about 45% or lessthan or equal to 50% of the thickness of the thinner of the first andsecond layers.

The composition comprising a metal that is electrodeposited onto thearticle may vary in its constituent metals. In some embodiments, thecomposition comprises one or more, two or more, three or more, or fouror more different metals independently selected from Ag, Al, Au, Be, Co,Cr, Cu, Fe, Hg, In, Mg, Mn, Mo, Nb, Nd, Ni, Pd, Pt, Re, Rh, Sb, Sn, Mn,Pb, Ta, Ti, W, V, Zn and Zr, wherein each of said independently selectedmetals is present at greater than 0.1, 0.05, 0.01, 0.005 or 0.001% byweight.

In other embodiments, the composition electrodeposited onto the articlecomprises two or more or three or more different metals independentlyselected from Ag, Al, Au, Be, Co, Cr, Cu, Fe, Hg, In, Mg, Mn, Mo, Nb,Nd, Ni, Pd, Pt, Re, Rh, Sb, Sn, Mn, Pb, Ta, Ti, W, V, Zn and Zr, whereineach of said independently selected metals is present at more than 0.1,0.05, 0.01, 0.005, or 0.001% by weight. In such embodiments,compositions of two or more different metals that can beelectrodeposited comprise, for example, Zn and Fe, Zn and Ni, Co and Ni,Ni and Fe, Ni and Cr, Ni and Al, Cu and Zn, or Cu and Sn.

In some embodiments, the composition electrodeposited onto the articlecomprises a structurally and/or compositionally modulatedelectrodeposited material or composition. The structurally and/orcompositionally modulated composition may comprise at least one portionhaving a plurality of layers deposited with wavelengths between about 1nm and about 250 nm, about 1 nm and about 25 nm, about 5 nm and about 50nm, about 10 nm and about 75 nm, about 1 nm and about 100 nm, about 2 nmand about 200 nm, about 5 nm and about 225 nm or about 10 nm and about250 nm.

In other embodiments, the structurally and/or compositionally modulatedmaterial has at least one portion consisting of a plurality of layers,wherein each of said layers has a thickness in a range selectedindependently from about 5 nm to about 250 nm, from about 5 nm to about25 nm, from about 10 nm to about 30 nm, from about 30 nm to about 60 nm,from about 40 nm to about 80 nm, from about 75 nm to about 100 nm, fromabout 100 nm to about 120 nm, from about 120 nm to about 140 nm, fromabout 140 nm to about 180 nm, from about 180 nm to about 200 nm, fromabout 200 nm to about 225 nm, from about 220 nm to about 250 nm or fromabout 150 nm to about 250 nm.

As described above, where the electrodeposited material comprises two ormore structurally and/or compositionally different layers, the layersmay have discrete or diffuse interfaces.

In embodiments where the electrodeposited material comprises two or morestructurally and/or compositionally different layers, the material maycomprise a plurality of alternating first layers and second layers. Thecoating of electrodeposited material may consist entirely of thealternating first and second layers, which may have discrete or diffuseinterfaces between the layers. Alternatively, one or more additionallayers may be present in the coating between any first and second layer.

In embodiments where the electrodeposited composition applied to all orpart of the article comprises a plurality of layers (e.g., first layersand second layers or alternating first and second layers), theelectrodeposited composition applied to the article (e.g., as aconformal coating or partial coating) may comprise two or more, three ormore, four or more, six or more, eight or more, ten or more, twenty ormore, forty or more, fifty or more, 100 or more, 200 or more, 500 ormore, 1,000 or more, 1,500 or more or 2,000 or more alternating firstand second layers independently selected for each multilayer coating.

Coatings comprising nickel and cobalt described herein can be applied tothe conductive surfaces of articles by electrodeposition as describedabove. In some embodiments, the electrodeposition of a coating used toimprove the properties of an article is carried out in a single bath.Such processes generally comprise the steps of:

-   -   a) placing the article in contact with a first electrolyte        comprising a salt of nickel, cobalt and optionally comprising        any other species of metal to be electrodeposited;    -   b) applying electric current and varying in time one or more of:        the amplitude of the electrical current, electrolyte        temperature, electrolyte additive concentration, or electrolyte        agitation, in order to produce first and second layers of        electrodeposited materials differing in their elemental        composition; and    -   c) growing the coating under such conditions until the desired        thickness of the coating is achieved.

Nanolaminated nickel-cobalt coatings can also be applied to theconductive surfaces of articles by electrodeposition using serialelectrodeposition in two or more baths. Such processes includeelectrodepositing each first and second layer in separate baths byalternately electrodepositing layers in each bath. Alternatively,nanolaminate layers may be formed by: serially electrodepositing aseries of first and second layers from a first electrolyte comprising asalt of nickel, cobalt and any other species of metal to beelectrodeposited by varying in time one or more of: the amplitude of theelectrical current, electrolyte temperature, electrolyte additiveconcentration, or electrolyte agitation; followed by seriallyelectrodepositing a series of first and second layers from a secondelectrolyte comprising a salt of nickel, cobalt and any other species ofmetal to be electrodeposited by varying in time one or more of: theamplitude of the electrical current, electrolyte temperature,electrolyte additive concentration, or electrolyte agitation.

Accordingly one process employing two different electrolytes forelectrodepositing a nanolaminate nickel coating may comprise the stepsof:

-   -   a) placing an article in contact with a first electrolyte        comprising a salt of nickel or salts of nickel and cobalt, and        optionally comprising any other species of metal to be        electrodeposited;    -   b) applying electric current to electrodeposit a first layer;    -   c) contacting the article with a second electrolyte bath        comprising a salt of nickel or salts of nickel and cobalt, and        optionally comprising any other species of metal to be        electrodeposited;    -   d) applying electric current to electrodeposit a second layer        that is different in composition from said first layer; and    -   e) repeating steps (a) through (d) until the desired thickness        of the multilayer coating is achieved;

wherein steps (a) through (d) are repeated at least two times.

In other embodiments, a nickel-cobalt coating may be electrodeposited bya process employing two different electrolytes to deposit thenanolaminate coating layers comprising the steps of:

-   -   a) placing an article in contact with a first electrolyte        comprising a salt of nickel or salts of nickel and cobalt, and        optionally comprising any other species of metal to be        electrodeposited;    -   b) applying electric current and varying in time one or more of:        the amplitude of the electrical current, electrolyte        temperature, electrolyte additive concentration, or electrolyte        agitation, in order to produce first and second layers of        electrodeposited materials differing from each other in their        elemental composition and to electrodeposit a first nanolaminate        coating;    -   c) repeating steps (a) through (b) until the desired thickness        of the multilayer coating is achieved;    -   d) contacting the article with a second electrolyte bath        comprising a salt of nickel or salts of nickel and cobalt, and        optionally comprising any other species of metal to be        electrodeposited;    -   e) applying electric current and varying in time one or more of:        the amplitude of the electrical current, electrolyte        temperature, electrolyte additive concentration, or electrolyte        agitation, in order to produce a second set of first and second        layers of electrodeposited materials differing in their        elemental composition from each other and to electrodeposit a        second nanolaminate coating differing in composition from the        nanolaminate coating produced by steps (a) through (c); and    -   f) repeating steps (d) through (e) until the desired thickness        of a multilayer coating is achieved.

8.0 Certain Embodiments

1. A method of coating an article comprising:

applying to all or part of a surface of said article one or moreelectrodeposited multilayered coatings comprising a plurality ofalternating first layers of nickel or an alloy comprising nickel, andsecond layers of an alloy comprising nickel and cobalt to form a coatedarticle;

wherein said one or more multilayer coatings comprises from about 50 toabout 100, from about 100 to about 1,000, from about 1,000 to about2,000, from about 2,000 to about 4,000, from about 4,000 to about 8,000or greater than 8,000 alternating first and second layers independentlyselected for each multilayer coating;

wherein each of said first layers and each of said second layers have athickness in a range selected independently from about 5 nm to about 200nm, from about 5 nm to about 25 nm, from about 10 nm to about 30 nm,from about 30 nm to about 60 nm, from about 40 nm to about 80 nm, fromabout 75 nm to about 100 nm, from about 100 nm to about 120 nm, fromabout 120 nm to about 140 nm, from about 140 nm to about 180 nm, fromabout 180 nm to about 200 nm or from about 200 to about 250 nm; andwherein the burst pressure and collapse pressure of said coated articleare increased relative to said article or a substantially identicalarticle having the same overall dimensions and composition but uncoated.

2. The method of embodiment 1, wherein said surface is an interiorsurface or an exterior surface, and wherein for at least one multilayercoating said first layer is in contact with said interior surface orexterior surface.3. The method of any of embodiments 1-2, wherein said surface is aninterior surface or an exterior surface, and wherein for at least onemultilayer coating said second layer is in contact with said interiorsurface or exterior surface.4. The method of any of embodiments 1-3, wherein each said first layercomprises greater than about 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%,90%, 92%, 93%, 94%, 95%, 96%, 97%, 98% or 99% nickel.5. The method of any of embodiments 1-4, wherein each second layercomprises cobalt in a range independently selected from 5%-35%, 5%-10%,10%-15%, 15%-20%, 20%-25%, 25%-30%, or 30%-35%.6. The method of embodiment 4, wherein each first layer comprises nickelin a range selected independently from 50%-55%, 55%-60%, 60%-65%,65%-70%, 70%-75%, 75%-80%, 80%-85%, 85%-90%, 90%-92%, 92%-93%, 93%-94%,94%-95%, 95%-96%, 96%-97%, 97%-98% or 98%-99% and the balance of thelayer is cobalt.7. The method of embodiment 5, wherein each second layer comprisescobalt in a range selected independently from 5%-35%, 5%-10%, 10%-15%,15%-20%, 20%-25%, 25%-30%, or 30%-35% and the balance of the layer isnickel.8. The method of any of embodiments 1-5, wherein one or more of saidfirst and/or second layers comprises one or more, two or more, three ormore or four or more elements selected independently for each layer ofeach coating from the group consisting of Ag, Al, Au, Be, C, Cr, Cu, Fe,Hg, In, Mg, Mn, Mo, Nb, Nd, Pd, Pt, Re, Rh, Sb, Si, Sn, Pb, Ta, Ti, W,V, Zn and Zr.9. The method of any of embodiments 1-8, wherein each of said elementsare present at concentrations of 0.01% or greater.10. The method of any of embodiments 1-8, wherein each of said one ormore electrodeposited coatings has a thickness in a range selectedindependently from 1 micron to 5 cm, from 1 micron to 50 microns, from50 microns to 100 microns, from 100 microns to 200 microns, from 200microns to 500 microns, from 500 microns to 800 microns, from 800microns to 1.2 mm, from 500 microns to 1 mm, from 1 mm to 1.5 mm, from1.2 mm to 2 mm, from 1.8 mm to 2.5 mm, from 2 mm to 3 mm, from 2.5 mm to5 mm, from 1 mm to 5 mm, from 5 mm to 1 cm, from 1 cm to 2 cm or from 2cm to 5 cm.11. The method of any of embodiments 1-10, wherein said article isformed from a steel alloy comprising: carbon and iron; carbon, iron,molybdenum; or carbon, iron, molybdenum and cobalt.12. The method of any of embodiments 1-11, wherein said article is apipe or tube having a composition, comprising a wall, an interiorsurface, and an exterior surface defining an exterior diameter, andhaving an exterior diameter/wall thickness (D/T) ratio;

said method further comprising applying the multilayer coating to atleast one of the interior and/or exterior surfaces to form a coatedpipe;

wherein when the D/T ratio is from about 14 to about 15 the burstpressure and/or collapse pressure of the coated pipe is increased fromabout 5% to about 22%, from about 5% to about 10%, from about 10% toabout 15% or from about 15% to about 22% relative to an uncoated pipehaving said composition and substantially the same D/T ratio as thecoated pipe; and

wherein when the D/T ratio is from about 15 to about 21 the burstpressure and/or collapse pressure of the coated pipe is increased fromabout 10% to about 36%, from about 10% to about 15%, from about 15% toabout 20%, from about 20% to about 25%, from about 25% to about 30% orfrom about 30% to about 36% relative to an uncoated pipe having saidcomposition and substantially the same D/T ratio as the coated pipe.

13. The method of embodiment 12, wherein the coated pipe has a D/T ratioof about 15, and the collapse pressure is greater than about 13,000 psi.14. The method of embodiment 12, wherein the coated pipe has a D/T ratioof about 16 and the collapse pressure is greater than about 11,000 psi.15. The method of embodiment 12, wherein the coated pipe has a D/T ratioof about 17 and the collapse pressure is greater than about 10,500 psi.16. The method of embodiment 12, wherein the coated pipe has a D/T ratioof about 18 and the collapse pressure is greater than about 9,750 psi.17. The method of embodiment 12, wherein the coated pipe has a D/T ratioof about 19 and the collapse pressure is greater than about 9,000 psi.18. The method of embodiment 12, wherein the coated pipe has a D/T ratioof about 20 and the collapse pressure is greater than about 8,600 psi.19. The method of embodiment 12, wherein the coated pipe has a D/T ratioof about 21 and the collapse pressure is greater than about 8,000 psi.20. An article prepared by the method of any of embodiments 1-19.21. A pipe having a substantially cylindrical shape comprising:

a wall comprised of a material having a composition, an interiorsurface, and an exterior surface;

said pipe having dimensions including a wall thickness, an innerdiameter defined by said interior surface, and an exterior diameterdefined by said exterior surface;

where at least one of said interior surface and said exterior surfacecomprises an electrodeposited multilayered coating;

said pipe having a burst pressure and a collapse pressure, wherein saidburst pressure and/or collapse pressure of said pipe is greater than thecollapse pressure and/or burst pressure of a pipe having substantiallythe same composition and dimensions in the absence of a coating on itsinterior or exterior surface.

22. The pipe according to embodiment 21, wherein said multilayeredcoating comprises a plurality of alternating first layers of nickel oran alloy comprising nickel, and second layers of an alloy comprisingnickel and cobalt.23. The pipe of any of embodiments 21-22, wherein said multilayercoating comprise from about two to about 50, from about 50 to about 100,from about 100 to about 1,000, from about 1,000 to about 2,000, fromabout 2,000 to about 4,000, from about 4,000 to about 8,000 or greaterthan 8,000 alternating first and second layers independently selectedfor each multilayer coating.24. The pipe of any of embodiments 21-23, wherein said first layers eachhave a thickness in a range selected independently from about 5 nm toabout 200 nm, from about 5 nm to about 25 nm, from about 10 nm to about30 nm, from about 30 nm to about 60 nm, from about 40 nm to about 80 nm,from about 75 nm to about 100 nm, from about 100 nm to about 120 nm,from about 120 nm to about 140 nm, from about 140 nm to about 180 nm,from about 180 nm to about 200 nm or from about 200 nm to about 250 nm.25. The pipe of any of embodiments 21-24, wherein said second layerseach have a thickness in a range selected independently from about 5 nmto about 200 nm, from about 5 nm to about 25 nm, from about 10 nm toabout 30 nm, from about 30 nm to about 60 nm, from about 40 nm to about80 nm, from about 75 nm to about 100 nm, from about 100 nm to about 120nm, from about 120 nm to about 140 nm, from about 140 nm to about 180nm, from about 180 nm to about 200 nm or from about 200 nm to about 250nm.26. The pipe of any of embodiments 21-25, wherein for at least one ofsaid electrodeposited multilayered coatings said first layer is incontact with said interior surface or said exterior surface.27. The pipe of any of embodiments 21-25, wherein for at least one ofsaid electrodeposited multilayered coatings said second layer is incontact with said interior surface or said exterior surface.28. The pipe of any of embodiments 21-27, wherein each first layercomprises nickel in a range independently selected from: 50%-55%,55%-60%, 60%-65%, 65%-70%, 70%-75%, 75%-80%, 80%-85%, 85%-90%, 90%-92%,92%-93%, 93%-94%, 94%-95%, 95%-96%, 96%-97%, 97%-98% and 98%-99%.29. The pipe of any of embodiments 21-28, wherein each second layercomprises cobalt in a range independently selected from: 5%-35%, 5%-10%,10%-15%, 15%-20%, 20%-25%, 25%-30%, and 30%-35% cobalt.30. The pipe of embodiment 28, wherein each first layer comprises nickelin a range independently selected from: 50%-55%, 55%-60%, 60%-65%,65%-70%, 70%-75%, 75%-80%, 80%-85%, 85%-90%, 90%-92%, 92%-93%, 93%-94%,94%-95%, 95%-96%, 96%-97%, 97%-98% and 98%-99%; and wherein the balanceof the second layer is cobalt.31. The pipe of embodiment 29, wherein each second layer comprisescobalt in a range selected independently from: 5%-35%, 5%-10%, 10%-15%,15%-20%, 20%-25%, 25%-30%, or 30%-35%; and wherein the balance of thelayer is nickel.32. The pipe of any of embodiments 21-29, wherein one or more of saidfirst and/or second layers comprises one or more, two or more, three ormore or four or more elements selected independently for each layer fromthe group consisting of Ag, Al, Au, Be, C, Cr, Cu, Fe, Hg, In, Mg, Mn,Mo, Nb, Nd, Pd, Pt, Re, Rh, Sb, Si, Sn, Pb, Ta, Ti, W, V, Zn and Zr.33. The pipe of embodiment 32, wherein each of said elements is presentat a concentration of 0.01% or greater.34. The pipe of any of embodiments 21-33, comprising from about 50 toabout 100, from about 100 to about 1,000, from about 1,000 to about2,000, from about 2,000 to about 4,000, from about 4,000 to about 8,000,from about 8,000 to about 10,000, or 10,000 or more alternating firstand/or second layers.35. The pipe of any of embodiments 21-35, wherein each saidelectrodeposited coating on said interior and/or exterior surface has athickness in a range selected independently from 1 micron to 5 cm, from1 micron to 50 microns, from 50 microns to 100 microns, from 100 micronsto 200 microns, from 200 microns to 500 microns, from 500 microns to 800microns, from 800 microns to 1.2 mm, from 500 microns to 1 mm, from 1 mmto 1.5 mm, from 1.2 mm to 2 mm, from 1.8 mm to 2.5 mm, from 2 mm to 3mm, from 2.5 mm to 5 mm, from 1 mm to 5 mm, from 5 mm to 1 cm, from 1 cmto 2 cm or from 2 cm to 5 cm.

1. A method of coating an article comprising: applying to all or part ofa surface of said article one or more electrodeposited multilayeredcoatings comprising a plurality of alternating first and second layersof to form a coated article, said first layers comprising nickel or analloy comprising nickel; and said second layers comprising an alloy ofnickel and cobalt; wherein said one or more multilayer coatingscomprises from about 50 to about 100, from about 100 to about 1,000,from about 1,000 to about 2,000, from about 2,000 to about 4,000, fromabout 4,000 to about 8,000 or greater than 8,000 alternating first andsecond layers independently selected for each multilayer coating;wherein each of said first layers and each of said second layers have athickness in a range selected independently from about 5 nm to about 200nm, from about 5 nm to about 25 nm, from about 10 nm to about 30 nm,from about 30 nm to about 60 nm, from about 40 nm to about 80 nm, fromabout 75 nm to about 100 nm, from about 100 nm to about 120 nm, fromabout 120 nm to about 140 nm, from about 140 nm to about 180 nm, fromabout 180 nm to about 200 nm or from about 200 to about 250 nm; andwherein the burst pressure and collapse pressure of said coated articleare increased relative to said article or a substantially identicalarticle having the same overall dimensions and composition but uncoated.2.-3. (canceled)
 4. The method of claim 1, wherein each said first layercomprises greater than about 50% nickel by weight.
 5. The method ofclaim 1, wherein each second layer comprises cobalt in a range from 5%to 35% by weight. 6.-7. (canceled)
 8. The method of claim 1, wherein oneor more of said first and/or second layers comprises one or more, two ormore, three or more or four or more elements selected independently foreach layer of each coating from the group consisting of Ag, Al, Au, Be,C, Cr, Cu, Fe, Hg, In, Mg, Mn, Mo, Nb, Nd, Pd, Pt, Re, Rh, Sb, Si, Sn,Pb, Ta, Ti, W, V, Zn and Zr.
 9. (canceled)
 10. The method of claim 1,wherein each of said one or more electrodeposited coatings has athickness in a range from 1 micron to 5 cm.
 11. (canceled)
 12. Themethod of claim 1, wherein said article is a pipe or tube having acomposition, comprising a wall, an interior surface, and an exteriorsurface defining an exterior diameter, and having an exteriordiameter/wall thickness (D/T) ratio; said method further comprisingapplying the multilayer coating to the interior and/or exterior surfacesto form a coated pipe; wherein when the D/T ratio is from about 14 toabout 15 the burst pressure and/or collapse pressure of the coated pipeis increased from about 5% to about 22%, from about 5% to about 10%,from about 10% to about 15% or from about 15% to about 22% relative toan uncoated pipe having said composition and substantially the same D/Tratio as the coated pipe; and wherein when the D/T ratio is from about15 to about 21 the burst pressure and/or collapse pressure of the coatedpipe is increased from about 10% to about 36%, from about 10% to about15%, from about 15% to about 20%, from about 20% to about 25%, fromabout 25% to about 30% or from about 30% to about 36% relative to anuncoated pipe having said composition and substantially the same D/Tratio as the coated pipe. 13.-18. (canceled)
 19. The method of claim 12,wherein the coated pipe has a D/T ratio of about 21 and the collapsepressure is greater than about 8,000 psi.
 20. An article prepared by themethod of claim
 1. 21. A pipe having a substantially cylindrical shapecomprising: a wall comprised of a material having a composition, aninterior surface, and an exterior surface; said pipe having dimensionsincluding a wall thickness, an inner diameter defined by said interiorsurface, and an exterior diameter defined by said exterior surface;where at least one of said interior surface and said exterior surfacecomprises an electrodeposited multilayered coating; said pipe having aburst pressure and a collapse pressure, wherein said burst pressureand/or collapse pressure of said pipe is greater than the collapsepressure and/or burst pressure of a pipe having substantially the samecomposition and dimensions in the absence of a coating on its interioror exterior surface.
 22. The pipe according to claim 21, wherein saidmultilayered coating comprises a plurality of alternating first layersand second layers, said first layers comprising nickel or an alloycomprising nickel and said second layers comprising an alloy of nickeland cobalt.
 23. (canceled)
 24. The pipe of claim 21, wherein said firstlayers each have a thickness in a range selected independently fromabout 5 nm to about 200 nm or from about 200 nm to about 250 nm.
 25. Thepipe of claim 21, wherein said second layers each have a thickness in arange selected independently from about 5 nm to about 200 nm or fromabout 200 nm to about 250 nm. 26.-27. (canceled)
 28. The pipe of claim21, wherein each first layer comprises nickel in a range from 50%-55%,55%-60%, 60%-65%, 65%-70%, 70%-75%, 75%-80%, 80%-85%, 85%-90%, 90%-92%,92%-93%, 93%-94%, 94%-95%, 95%-96%, 96%-97%, 97%-98% and 98%-99% byweight. 29.-30. (canceled)
 31. The pipe of claim 21, wherein each secondlayer comprises cobalt in a range from 5%-35%.
 32. The pipe of claim 21,wherein one or more of said first and/or second layers comprises one ormore, two or more, three or more or four or more elements selectedindependently for each layer from the group consisting of Ag, Al, Au,Be, C, Cr, Cu, Fe, Hg, In, Mg, Mn, Mo, Nb, Nd, Pd, Pt, Re, Rh, Sb, Si,Sn, Pb, Ta, Ti, W, V, Zn and Zr. 33.-34. (canceled)
 35. The pipe ofclaim 21, wherein each said electrodeposited coating on said interiorand/or exterior surface has a thickness in a range from 1 micron to 5cm.